1,3,5-triazinediones

ABSTRACT

1,3,5-Triazinediones of the formula   WHEREIN X1, X2, R1, R2 and R3 are as hereinafter defined, are useful for the selective control of weeds in crops, e.g., corn. Many are also useful for altering plant flowering and plant sexual reproduction. Examplary of the class of compounds are 3-isopropyl-6methylthio-s-triazine-2,4(1H,3H)-dione, 3-(p-chlorophenyl)-6methoxy-s-triazine-2,4(1H,3H)-dione.

Ilnited States Patent 1191 Fuchs et al.

1111 3,855,219 5] Dec. 17, 1974 i 54 i 1,3,5-TRIAZINEDIONES [75] Inventors: Julius Jakob Fuchs, Wilmington;

Kang Lin, Newark, both of Del.

[73] Assignee: E. l. du Pont de Nemours and Company, Wilmington, Del.

[22] Filed: Oct. 30, 1972 [21] Appl. No.: 301,853

Related US. Application Data [63] Continuation-impart of Ser. No. 268,767, July 3, 1972, abandoned, which is a continuation-in-part of Ser. No. 181,202, Sept, 16, I971, abandoned.

[52] US. Cl 260/248 NS, 71/93, 260/455 A,

260/482 C, 260/552 R, 260/553 R [SI] Int. Cl C07d 55/50 [58] Field of Search 260/248 NS [56] References Cited UNITED STATES PATENTS 3,470,175 /1969 Weisboeck 260/248 3,505,057 4/1970 Luckenbaugh 260/248 X FOREIGN PATENTS OR APPLICATIONS 1,083,752 9/1967 Great Britain 1,912,226 11/1970 Germany Primary Examiner-John M. Ford [57] ABSTRACT l,3,5 -Triazinediones of the formula wherein X X R R and R are as hereinafter de- V 19 Claims, No Drawings 1 1,3,5-TRIAZINEDIONES CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of our application Ser. No. 268,767, filed July 3, 1972, which in turn is a continuation-in-part of our application Ser. No. 181,202, filed Sept. 16, 1971, both now aban' doned.

BACKGROUND OF THE INVENTION A This invention relates to s-triazine herbicides.

Neumayer et al., Pesticides, Chemical Week, April 12 and 26, 1969, lists several commercial and experimental s-triazine herbicides. Among these are prometone and prometryne, which have the structural formulae:

C|)CH3 SCHa on, N N CH; on, N N CH, Hist l H first, lair, I H N H 1 l H N H &

CH: Ha CH3 CH3 prometryne prometone These and related compounds are disclosed in U.S. Pat. No. 2,909,420.

SUMMARY OF THE INVENTION It has now been discovered that compounds of formula l are useful as selective herbicides for controlling broadleaf and grass weeds in such crops as rice, asparagus and corn. Many of the compounds are also useful, at lower rates of application, for altering plant flowering and plant sexual reproduction.

wherein R, is alkyl of 1 through 8 carbon atoms, cycloalkyl of 3 through 8 carbon atoms, cycloalkylalkyl of 4 through 7 carbon atoms, alkenyl of 3 through 4 carbon atoms, alkynyl of 3 through 4 carbon atoms, benzyl or Q is hydrogen, halogen, or methyl; R is hydrogen, a group where A is alkyl of 1 through 3 carbon atoms or alkoxy or all-tylthio of 1 through 4 carbon atoms, or a cation selected from lithium, sodium, potassium, calcium, magnesium, barium, or

N Ro Ra where R R and R, can be the same or different and each can be hydrogen, alkyl of 1 through 4 carbon atoms, or hydroxy alkyl of 2 through 4 carbon atoms; and R is hydrogen, alkyl of 1 through 12 carbon atoms, or benzyl; R and R can be taken together to form a ring that is (CI-I --O(CH or (CI-l where n is 4-6 and R and R are H; R is SR or 0R where R is alkyl of 1 through 6 carbon atoms, cycloalkyl of 3 through 6 carbon atoms, alkenyl or 3 through 4 carbon atoms, alkynyl of 3 through 4 carbon atoms, or benzyl, and X and X are oxygen or sulfur. Preferred within the above formula because of ease of synthesis and higher herbicidal activity are the com pounds where:

R is alkyl of 3 through 6 carbon atoms or alkenyl of.

3 through 4 carbon atoms; R is hydrogen;

R is SR or 0R R is alkyl of 1 through 6 carbon atoms or alkenyl of 3 through 4 carbon atoms; and X and X are oxygen. More preferred because of their highest herbicidal activity are those compounds of the formula where:

R, is alkyl of 3 through 4 carbon atoms; R is hydrogen; R is SCI-I SC H OCI-l or OC I-I and X, and X are oxygen. Preferred herbicidal compounds within the above formula include:

3-tert-butyl-6-methylthio-s-triazine-Z,4( 1 l-l,3H dione 3-secbutyl--methylthio-s-trimine-2,4( ll-l,3l-l)-dione 3-isopropyl-6-methylthio-s-triazine-2,4( lH,3I-l)-dione 3-isopropyl-6-methoxy-s-triazine-2,4( l l-l,3l-I )-dione 3-isopropyl-6-ethoxy-s-triazine-2,4( 1H,3H )-dlone Preferred for altering plant flowering and/or plant sexual reproduction are those compounds of Formula 1, R is methyl or ethyl, Y is hydrogen, halogen or methyl, 2 is halogen, and Q is hydrogen.

Most preferred for altering plant flowering and/or plant sexual reproduction are:

1 3-( 4-chlorophenyl-6-methylthio-s-triazine- 2,4( lH,3l-l)-dione 2 3-(4-chlorophenyl)-6-methoxy-s-triazine- DETAILED DESCRIPTION OF THE INVENTION Ra X1 l a z aiaN II ll CIIaOII CIIJONZL wherein R, R X and X are as previously defined.

The synthesis of allophanimidates and 3-thioallophanimidates from pseudourea and the synthesis of l-thioallophanimidates and l,3-dithioallophanimidates from thiopseudourea (Equation 1) can be performed analogous to a procedure given in Organic Synthesis 42, 87 which described the preparation of methyl 4- phenyl-3-thioallophanimidate l-phenyl-2-thio-4- methylisobiuret).

The reaction products of equation (1) are reacted at about 045C in a solvent, e.g. methylene chloride, with one equivalent of a chloroformate or a chlorothiolformate in the presence of one equivalent of a base such as triethylamine (Equations 20 and 2b). After completion of the reaction, the methylene chloride solution is washed with water, dried, and the solvent evaporated. to give alkoxycarbonylallophanimidates, alkylthiolcarbonylallophanimidates, alkoxycarbonylthioallophanimidates, alkylthiolcarbonylthioallophanimidates, alkoxycarbonyldithioallophanimidates and alkylthiolcarbonyldithioallophanimidates. Using a chlorodithioformate in the above reaction affords the corresponding alkylthiolthiocarbonylallophanimidates, alkylthiolthiocarbonylthioallophanimidates and alkylthiolthiocarbonyldithioallophanimidates. The reaction products of Equation (2a) and Equation (2b) are then refluxed for a sufficient time with a base such as sodium methoxide in methanol to effect cyclization (Equations 3a and 3b). The solvent is then evaporated under vacuum and the residue dissolved in water. Acidification of the aqueous solution usually precipitates the desired s-triazinediones. thio-striazinediones or s-triazinedithiones as an substantially pure solid.

The reaction products of Equations (2a) and (2b) are also obtained by reacting the pseudourea or thiopseudourea first with a chloroformate, a chlorothiolformate or a chlorodithioformate as in Equations (4a) and (4b), and then reacting the reaction products of Equations (4a) and (4b) with an isocyanate or isothiocyanate as in Equations (5a) and (5b).

The s-triazinediones form salts which are useful alone or can be reacted with an acyl chloride, an alkyl chloroformate, or an alkyl chlorothiolformate to give 1 -substituted analogs as illustrated by the following equations:

n u ll RiN N A-cc1 R1N N al al Na J:

where A is an alkyl, alkylthio or alkoxy group.

The following examples are offered to illustrate the processes described above. All parts are parts by weight unless otherwise indicated.

EXAMPLE 1 3-tert-Butyl-6-methylthio-s-triazine-2,4( lH,3H)-dione To a solution of 139 parts of 2-methyl-2- thiopseudourea sulfate in 1,000 parts of 50% aqueous methanol at 0C is added dropwise 88 parts of 50% sodium hydroxide, followed by 90 parts tert-butyl isocyanate in 200 parts tetrahydrofuran. The solution is concentrated at reduced pressure and filtered to yield, after drying, 90 parts of methyl 4-tert-butyl-1-thioallophanimidate melting at 102-l04C.

To a solution of 5.67 parts of the above compound and 4 parts of triethylamine 50 parts methylene chloride at 0C is added dropwise 3.3 parts methyl chlorothiolformate in 5 parts of methylene chloride. The solution is stirred overnight and washed once with water. After drying and evaporation of the solvent, there is ob tained 3.8 parts methyl 4-tert-butyl-N- methylthiolcarbonyl-l-thioallophanimidate melting at l02 l05C.

A solution of five parts of the above compound in 50 parts of methanol containing 3 parts of sodium methoxide is refluxed for one hour. The reaction mixture is then cooled and the methanol is evaporated at reduced pressure. One hundred parts of water are added and the solution twice extracted with 50 parts of ether. The aqueous layer is then neutralized at 0 to 5C with hydrochloric acid and extracted with methylene chloride. The methylene chloride extract is dried and the solvent evaporated to give 3 parts of 3-tert-butyl-6-methylthios-triazine-2,4( lH,3H)-dione, melting at 17l21 C.

EXAMPLE 2 3-Isopropyl-6-methylthio-s-triazine-2,4( lH,3H)-dione To a solution of 69.5 parts of 2-methyl-2- thiopseudourea sulfate and 47 parts of methyl chloroformate in 1,000 parts of water at 0C is added dropwise 56.9 parts of potassium hydroxide in 200 parts of water. The reaction mixture is stirred at room temperature for 3 hours and then extracted with methylene chloride. The methylene chloride extract is dried and the solvent evaporated at reduced pressure to give 45 g of methyl N-( l-amino-l-methylthiomethylene)- carbamate melting at 72-77C.

A solution of seventy-four parts of the above compound and 47 parts of isopropyl isocyanate in 300 parts methylene chloride is stirred overnight. The solvent is evaporated to give 113.6 parts of methyl 4-isopropy1- N-methoxycarbonyl-l-thioallophanimidate melting at l29-l 32C.

A solution of one hundred parts of the above compound in 200 parts of methanol containing 27 parts of sodium methoxide is refluxed for one hour. The methanol is evaporated under vacuum and the residue dissolved in 200 parts of water. The aqueous solution is neutralized with hydrochloric acid to afford after filtration and drying 55 parts of 3-isopropyl-6-methylthio-striazine-2,4( lH,3H)-dione melting at l88-l00C.

LII

EXAMPLE 3 parts of methyl N-(l-amino-l-methylthiomethylene)' thiolcarbamate melting at 7576C.

To a solution of 8.2 parts of the above compound in 75 parts of methylene chloride is added 3.1 parts of methyl isocyanate. The reaction mixture is stirred at room temperature for 3 hours, and then the solvent evaporated under vacuum to give 10 parts of methyl 4-methyl-N-methylthiolcarbonyll -thioallophanimidate melting at 1l5-l 17C.

A solution of six parts of the above compound in 75 parts of methanol containing 4.5 parts sodium methoxide is refluxed for 1 hour. The methanol is evaporated and the residue dissolved in water. The aqueous solution is then neutralized with hydrochloric acid at 0- 5C. The precipitate is collected by filtration and dried to give 2.3 parts of 3-methyl-6-methylthio-s-triazine- 2,4( lH,3H)-dione melting at 243244C.

EXAMPLE 4 3-(p-Chlorophenyl)-6-methylthio-s-triazine-2,4- (1H,3H)dione To a solution of 148 parts of methyl N-( lamino-lmethylthiomethylene)-carbamate, prepared as in Example 2, in 2,000 parts methylene chloride is added 154 parts of p-chlorophenyl isocyanate. The reaction is stirred for 3 days. Then to it is added 54 parts of sodium methoxide in 540 parts of methanol. The reaction mixture is then refluxed for 1 hour. The reaction mass is cooled, and 2,000 parts of ether are added. The solid collected by filtration is dissolved in water and the solution neutralized with hydrochloric acid. The new solid thus formed is collected, dried, and recrystallized from ethanol/H O to give parts of 3-(p-ch1orophenyl-6- methylthio-s-triazine-2,4(1H,3H)-dione melting at 292-295C.

EXAMPLE 5 3-sec-Butyl-6-methylthio-s-striazine-2,4( lH,3H )-dione To a solution of 7.2 parts of methyl N-( 1-amino-1- methylthiomethylene)carbamate, prepared as in Example 2, in 50 parts of methylene chloride is added 5.5 parts of sec-butyl isocyanate. The reaction mixture is stirred overnight and the solvent evaporated to give 12 parts of crude methyl 4-sec-butyl-N-methoxycarbonyll-thioallophanimidate melting at 102104C.

The above product is refluxed for 1 hour in parts of methanol containing 6 parts of sodium methoxide. The solvent is evaporated under vacuum and the residue is dissolved in 100 parts of water. The aqueous solution is extracted with methylene chloride and the aqueous layer then neutralized at 05C with hydrochloric acid. The aqueous solution is extracted again with methylene chloride. The extract is dried and the methylene chloride evaporated to give 7 parts of a solid melting at l24f-l32C. Recrystallization from chlorobutane gives 4 parts of 3-sec-butyl-6-methylthio-s- EXAMPLE 6 3-(p-Chlorophenyl)-6-methoxy-s-triazine-2,4( 1H,3H dione To 52 parts of 2-methylpseudourea hydrogen sulfate in 250 parts of water at -5C is added 31 parts of methyl chloroformate followed by dropwise addition of 74 parts of 50% sodium hydroxide. The reaction mass is stirred at room temperature for 3 hours and then extracted with methylene chloride. The methylene chloride extract is dried and the solvent evaporated. The residue is triturated with hexane to give 23 parts of methyl N-( l-aminol -methoxy-methylene)-carbamate melting at 36-39.5C.

To 13 parts of the compound prepared above in 200 ml of methylene chloride is added 15 parts of pchlorophenyl isocyanate. The reaction mass is stirred overnight. The solvent is evaporated and the residue refluxed overnight in 100 parts of 10% sodium methoxide in methanol. Water is added and the solution neutralized with hydrochloric acid. The crude solid collected by filtration is recrystallized from acetonitrile to give 7 parts of 3-(p-chlorophenyl)-6-methoxy-striazine-2,4(1H,3H)-dione melting at 23824lC.

EXAMPLE 7 3-(2-Methyl-4-chlorophenyl)-6-methoxy-s-triazine- 2,4(1H,3H)-dione To parts of methyl N-(l-amino-l-methoxymethylene)-carbonate prepared as in Example 6 in 200 parts of methylene chloride is added parts of 2-methyl-4-chlorophenyl isocyanate. It is stirred overnight and 8 parts sodium methoxide in parts of methanol is added. It is refluxed for 1 hour and the solid is collected by filtration. it is dissolved in water and the solution neutralized at 0-5C. with concentrated hydrochloric acid. The precipitate is collected by filtration to give 25 parts of 3-(2-mcthyl-4- chlorophenyl )-6-methoxy-s-triazine-2.4( 1H.3H )-dionc melting at l93-195C.

EXAMPLE 8 3-(0-Fluorophenyl)-6-methylthio-s-triazine- 2,4( lH,3H)-dione To a solution of 16 parts of methyl N-( l-amino-lmethylthiomethylene)carbamate, prepared as in Example 2, in parts of methylene chloride is added 15 parts of o-fluorophenyl) isocyanate. The reaction mixture is stirred overnight and the solvent evaporated to give after trituration with hexane 29 parts of methyl 4- (o-fluorophenyl )-N-methoxycarbonyl- 1 -thioallophanimidate melting at l23125C.

Sixteen parts of the above product are refluxed for 1 hour in 150 parts of methanol containing 9 parts of sodium methoxide. The solvent is evaporated under vacuum and the residue is dissolved in 200 parts of water. The aqueous solution is extracted with methylene chloride and the aqueous layer then neutralized at O-5C. with hydrochloric acid. The precipitate is collected and dried to give 1 1 parts of -3-(o-fluorophenyl)-6- methylthio-s-triazine-2,4(lH,3l-I)-dione melting at 196-l99C.

EXAMPLE 9 The following s-triazinediones can be prepared by the procedure of Example 2 by substituting the listed 2-substituted thiopseudoureas and pseudoureas, for 2- methyl -2-thiopseudourea, by using various chloroformates and by replacing isopropyl isocyanate with various isocyanates or isothiocyanates.

Thio seudourea lsocyanate or or eudourea lsothiocyanate Fomiates s-Tnazinediones 2-meth l-2-thio udourea eth lisoc anate methyl 3-eth l-6-meth lthio-s-triazine-ZA- y pse y y chloroformate (llgl,3H)-dioi ie, m.p. 190-l91 do. phenyl isodo. 3-phenyl-6-methy1thio-s-triazine-2.4-

c anate (11-1,3H)-dione, m. 235-245? do. cyc ohexyl isodo. 3-cyclohex l-6-rnethy thio-s-tnazmecyanate 2,4(1H, H)dione, m.p. 255-257 do. ofluoropheny1 do. 3-(o-fluorophenyl)-6-methylthio-s-triisocyanate azine-2,4(1H,3H)-dione, m.p. 19 6-199 do. onitrophenyl do. 3-(o-nitrophenyl)-6-methylthio-s-tnisocyanate azine-2,4(1H,3H)-dione, mp. 196-202 do. propyl isodo. 3-pro y1-6-methy1thio-s-triazme-2,4-

cyanate (1 .3H)-dione, m. 145- 148 do. m-tolyl isodo. 3-(m-tolylU-6-methylt io-s-tnazme-ZA- cyanate (1H,3 )-dione.m.p.176- do. allyl isocyanate do. 3-211lyl-6-methylthios-triazine-2,4(1H.3H)-

dione, mp. 140- 42 do. 3,4-dichlorophenyl do. 3-(3,4-dichbrophenyl)-6-methy1th|o-s-tria isocyanate zine-2.4(1H,3H)-dione, m. 269-271 do. p-fluorophenyl isodo. S-(p-fluorofirenyU--methyl io-s-triazinecyanate 2,4(1H,3 )-dione, mg. 239-243" do. p-nitrophenyl isodo. 3-(2p-nitrophenyl)-6-met ylthio-s-triazinecyanate ,4(1H,3H)-dione, mp. 279-280 2-methyl-2-thiopseudourea p-bromophenyl methyl 3-(iJ-bromofihenyD-6-meth lthio-s-triazineisocyanate chloroformate .4(1H,3 )-dione, m.p. 72273 do. o-chlorophenyl do. 3-(o-ch1orofihenyU-6-meth lthio-s-triazineisocyanate 2,4(1H,3 )-d1one. m.p. 12.5214 do. m-chlorophenyl do. 3-(m-chloro henyl)-6-meth lthio-s-triazineisocyanate 2,4(1H,3 )-dione, m.p. 92-l95.5 do. cyclohexylmethyl do. 3-c clohex lmethyl--meth lthio-s-triazineisocyanate ,4( 1H. H)-dione, m.p. 77.5-178 2-ullyl-2-thiopseudoisopropyl isodo. 3-isofiropyl-(r-allylthio-s-triztzine2,4-

urea cyunute (l .3 )-d|one, mp. 140-142" 2-mcthylpseudourcu phcnyl isocyunutc do. 3-phcny1-(i-mcth4ixy-s-triulinc-ZAt |Il.3H)-

dionc, mp. 198-201)" do. cyclohexyl isodo. 3-cycluhexy -b-meihoxy--s-triuzinc-Z.4-

cyanate (1H,3H)-dione, mp. 212-220 do. p-fluorophenyl do. 3-(2p-fluoro henylHi-methox -s-tria1ineisocyanate .4(1H 3 )-d|one, mp. 2 4-237 do. m-chlorophenyl do. B-(m-chloro henyl)-6-methox -s-triazineisocyanate 2,4(lH,3 )-dione. mp. 18 -185.5

Thiopseudourea Isocyanate or or Pseudourea lsothiocyanate Formates q i in diones Z-methylpseudo- ZA-dibromophenyl do. 3-( 2,4dibrom2phenyl )-6-methoxy-s-triazineurea lsocyanate 2.4( lH,3H) ione do. 2,5- d|chloro-4- do. 3-( 2,5-dichloro-4-nitrophenyl )-6-methoxymtrophenyl isos-triazine-2.4(1H.3H)-dione cyanate do. 3.4-diethoxyphenyl do. 3-( 3,4-diethoxyphenyl )-6-methoxy-sisoe anate triazine-2.4( lH.3H)-dione do. 2.4-di uorophenyl do. 3(2.4-difluoro hen l)-6-methoxy-sisocyanate triazine-2.4( Hjzll-dione do. 2.5-dimethoxyphenyl do. 3-(2.5-dimethoxv henyl)-6-methoxy-sisocyanate triazine-2 4(l .3H)-dione Z-methylpseudo- 3.5-dinitrophenyl isomethyl 3-(3.5-dinitrpphenyl)-6-methoxy-s-triuurea cyanate chloroformate zinc-2.4(l .3H)-dione do. 2-fluoro-4.6-dinitrodo. 3-(2-fluoro-4.6-dinitro henyU-fi-methoxyphenyl isocyanate s-triuzine-2 4( lH.3 )-dione do. 3-nitro-4fluorophenyl do. 3-(3-nitro-4fluoro hen 'l)-6 methoxy -sisocyanate triazine-2.4( lH.. H )-il0l16 do. 2-methyl-4-methoxyphenyl do. 3-(2-methyl-4-methofi henyl)-6-niethoxyisocyanate s-triazine-2.4( lH.3 i -dione do. 2-methoxy-4-nitrophenyl do. 3-( Z-methoxgA-nitronhenyl )-6-methoxyisocyanate s-trlazme- ,4( lH,3 )-dione do. 2,4,5-trichlorophenyl do. 3-( 2.4,5-trichlorophenyl )-6-methoxy-sisocyanate triazine-2.4( 1H,3H )-dione do. 2.4.6-trimethylphenyl do. 3-(2,4,6-trimeth lphenyl)-6-methoxy-sisocyanate triazine-2,4(l ,3H)-dione EXAMPLE 10 Lithium 3-iso rlopyl-6-methylthio-s-triazine-2,4-

Fl H)dione 3-lsopropyl-6-methylth1os-triazme-2,4( l H,3H )-dione Potassium 3450???-6-n' ethylthi0-s-triazine-2,4- To a solution of 138 parts of 2-methyl-2- l Calcium bis-3-(tert-but l)6-methylthio-s-triazlnethiopseudiourea sulfate in 500 parts of water IS added 2,4(1H3 Mime 80 parts 50% sodium hydroxide at 0-10C. One thou- Magnesium ;f fig gaz 'g)g gg y 0 n parts acetone are a i y a p Barium bis-3-(tert-but l)-6 -methylthio-s-triazinewise addition of 85 parts of isopropyl isocyanate at 0C. S04 3 3 W20 1 6 h Hf The reaction mixture is allowed to warm to room temmm ll i'lliggg yt KH- perature in 2 hours. The acetone is evaporated and the Sodium 3eyelpioic3 l-)6 C-!methyltgi& -Ctriazine-2,4-

lone, Solid 1S filtered and dried to give 150 parts m ethyl 4- Sodium HmtIuoroPhenYlyamethyhhiosqriaziw isopropyl-lthroallophammrdate melting at 81 85 C. I 2,4(lH.3H)-di0n. 300C.

To a solution of 3.9 parts of phosgene in 100 parts of sodum 1231$1f22"fgggclg benzene is added dropwise 8.7 parts of the above com- Sodium 3-(3-chloro-i-r iieltll ygngen i)-6-m6l(t))(')ll(l;l0-5- triazine-.., ione, pound in 50 parts of tetrahydrofuran. The reaction Sodium ulfidichlom henyl) 6 meth khicrsmw mixture IS heated to reflux, cooled, and 16 parts of 50% zi -2,4 1 ,3H .di(me 00C. sodium hydroxide in 100 parts of water added. After Sodwm q g gg gtgg g ggg heating the solution to reflux, the benzene layer is dissodium hyciohe t l.f rhyhhi g i i .z 4. carded and the aqueous layer is neutralized with hydro- 40 Mime 300C chloric acid to give after filtration and drying 2 parts of I 3-isopropyl-6-methylthio-s-triazine-2,4-( l H,3H )-dione EXAMPLE 12 melting at l88l90C.

EXAMPLE 1 1 Ammonium 3-(p-chlorophenyl)-6-methoxy-s-triazine- 2,4( lH,3H )-dione To a mixture of 10 parts-of 3-(p-chlorophenyI)-6- methoxy-s-triazine-2.4( lH,3H)-dione and l00 parts of methanol is added 1 part of ammonia gas at 20C. The solution is stirred for 30 minutes and then evaporated under vacuum to give 10.6 parts of ammonium 3-(pchlorophenyl )-6-methoxy-s-triazine-2,4( 1H,3 H dione.

Similarly, the following s-triazinedione amine salts can be prepared by using the appropriate starting materials.

methylammonium 3-( hloro hen l)-6-methox s-triazine- ZEiiIHJED-diime y tri-(2-hydroxydo. ethyl )ammoniu do. 3-iso r0 l-6-ethoxy-s-triazine-2,4-

l ,3 )-dione dimethylammonium o. ethylammonium do. morpholinium do.

giperidinium utylammomum do. 3-( hloro hen l)-6-meth lthio-s-trian'ne- {Rim )-dii ne y di-sec-butyldo. ammonium diethylammonium do. propylammonium do. hexah dro- 3-isopropyl-6-methoxy-s-triazine-2,4( 1H,3H)- azepi imum dione pyrrolidinium do. tetraethylammonium do. trimethylammonium 3-( 2-methyl-4-chlorophenyl )-6-methoxy-striazine-2.4( lH,3H)-dione tetramethylanunonium do. dodecyltnmethyldo. ammonium Z-hydroxyetl-nylarmnonium do. benzylammonium do. benzyltrimethyldo. ammonium triethylammonium do.

EXAMPLE l3 EXAMPLE l5 3-lsopropyl-6-ethoxy-s-triazin-Z,4( ll-l,3l-l )-dione To 114 parts of Z-methylpseudourea sulfate in 400 parts of water. at 0C is added 106 parts of sodium hydroxide, followed by 400 parts of acetone, and 51 parts of isopropyl, isocyanate. The reaction mixture is allowed to come to room temperature in 3 hrs. The organic solvent is then evaporated under vacuum, the aqueous residue saturated with sodium chloride, and the mixure extracted with methylene chloride. The organic extract is dried and the methylene chloride evaporated to 7 yield 78 parts of methyl 4- isopropylalophanimidate, m.p. 64-67C.

To a solution of 32 parts of the above compound and Starting s-triazinedione Halide Product 3-isopropyl-6-methylthiobutylil'yl' 1-butyryl-3-isopropyls-triazine-2.4(ll-l,3H)- c oride 6-methylthio-s-triadione zine-2,4( ll-l,3H)dione 3-isopropyl-6-ethoxyismethyl l-methoxycarbonyl-3- triazine-2.4(lH.3 chloroformate isopropyl-6ethox -sdione triazine-2,4(lH,3 )-dione 3 p-chlorophenyl )-6- methyl l-methylthiolcarbonyl-3- methoxys-triazinechlorothiol- (p-chlorophen l)-6-methoxy- 2.4( lH.3H)-dione formate s-triazine-2,4( H,3H)-

dione y do. n-hutyl l-butylcarbonyI-Ci-(pchlorofonnate chlorophen l)-6-methoxys-triazin-Z, (lH,3H)- dione 3-(2-methyl-4-chloron-butyl l-butylthiolcarbonyl-Iiphenyl)-6-meth lthiochlorothiol- (Z-meth l-{l-chlorophenyhs-triazin-2,4(l .3H)- 'formate 6-methy thios-tnazmedione 2,4( l H,3H)-dione EXAMPLE l4 3-lsopropyl-6-methoxy-s-triazine-2,4( 1H,3l-l )-dione A solution of 23 parts of methyl N-( l-amino-lmethoxymethylene)-carbamate, 16 parts of isopropyl isocyanate 60 parts of methylene chloride, and a catalytic amount of dimethylformamide and triethylamine is allowed to stand at room temperature for 3 days. The solvent is evaporated to afford 33 parts of crude methyl 4-isopropyl-N-methoxycarbonylallophanimidate, an oil N 1.4823.

A solution of 9 parts of the above compound, 10 parts of sodium methoxide, and 100 parts of methanol is refluxed for 1 hr. The solvent is removed under vacuum. Water is then added to the residue. After extraction with methylene chloride, the aqueous layer is neutralized at 5-l0C. Filtration affords 3 parts of crude solid, which is recrystallized from acetonitrile to give 2 parts of 3-isopropyl-4-methoxy-s-triazine-2,4( ll-l,3l-l)- dione m.p. l95200C.

24 parts of triethylamine at 0C is added 27 parts of ethyl chlorothiolformate. The reaction mixture is stirred at room temperature overnight. Water is added and the methylene chloride layer is separated and dried. The methylene chloride is then evaporated to yield 64 parts of crude methyl 4-isopropyl-N- ethylthiolcarbonylallophanimidate, an oil.

A solution of 64 parts of the above compound, 40 parts of sodium methoxide, and 500 parts of ethanol is refluxed for 1 hour. Ethanol is then removed under vacuum and water is added to the residue. After extraction with methylene chloride, the aqueous layer is neu- Formulation and Use of the Compounds The compounds of this invention are useful herbicides to selectively control weeds in crops such as field corn, sweet corn, rice, asparagus, established nursery stock and certain established fruit trees. The compounds can be applied preemergence, as a directed postemergence treatment or in certain specific cases as an overall postemergence treatment. Application rates range from Va to 10 kilograms/hectare. Method and rate of application depend upon such factors as crop, soil type, climatic condition and weed population. Uniform distribution of the compounds is important particularly in postemergence treatment.

These compounds may also be combined with other herbicides such as linuron, monuron, diuren, terbacil, and peraquat to control a broader spectrum of weeds.

The compounds of formula I can be formulated in the various ways which are conventional for herbicides of similar physical properties. Useful formulations include wettable and soluble powders, oil suspensions and solutions, aqueous dispersions, dusts, granules, pellets and high strength compositions. Broadly speaking, these formulations consist essentially of about 1 to 99% by weight of herbicidally active material fincludingat least onecompound of formula I in a herbicidally effective amount) and at least one of (a) about0.l to by weight of surface active agent and (b) about 5 to 99% by weight of essentially biologically inert solid or liquid diluent. More specifically, the various types of formulations will generally contain these ingredients in the following approximate proportions.

Percent By Weight The actual percentagesthat can be realized with a particular compound of formula I will depend upon its physical properties.

The manner of making and using such herbicidal formulations is described in numerous patents. See. for example, Luckenbaugh U.S. Pat. No. 3.309.192, Loux U.S. Pat. No. 3,235,357, Todd U.S. Pat. No. 2.655.445. Hamm et al. U.S. Pat. No. 2,863,752, Scherer et al. U.S. Pat. No. 3,079,244, Gysin et al. U.S.Pat. No. 2,891,855, and Barrous US. Pat. No. 2,642,354.

The herbicidal activity of compounds of this inven tion was discovered in a greenhouse test. In this test, seeds of crabgrass (Digiraria spp.), barnyurdgrass (Echinochloa crus-galli), wild oats (Avenefarua). C assiu tora, morningglory (Ipomoea spp.), radish (Raphanus spp.),marigold (Tagetes spp.), dock (Rumes crispus), bean, corn, soybean, rice, wheat and nutsedge tubers were planted in a growth medium and treated preemergence with the chemical dissolved in a non-phytotoxic solvent. At the same time cotton having five leavves (including cotyledonary ones), johnsongrass (Sorghum halepense) having four leaves, crabgrass and barnyardgrass with three leaves and. nutsedge (Cyperus rotundus) from tubers with two leaves were treated postemergence. Bush beans with the third trifoliate'leaf expanding and sorghum with four leaves were also treated postemergence. Treated plants and controls were maintained in a greenhouse for 16 days, then all species were compared to controls and visually rated for responses to treatment. A qualitative (type of plant response) rating was made. The letter C" indicates chlorosis; the letter B indicates burn; G" indicates growth retardation; D indicates defoliation; U" indicates unusual pigmentation; S indicates albinism; l indicates increased chlorophyll; EF indicates early flowering; DF indicates delayed flowering; X indicates axillary stimulation; A indicates growth acceleration; and Y indicates increased number of buds or flowers. A qualitative rating on a scale of O to 10 was also made; a rating of zero means no effect; a rating of 10 means maximum effect, e.g. complete kill in case of chlorosis. Results obtained in this test for some highly active compounds of this invention are given in the following table; in the table the ampersand Sy malds for the numegi 10. I

where A is alkyl of 1 through 3 carbon atoms or alkoxy or alkylthio of 1 through 4 carbon atoms. or a cation selected from lithium, sodium, potassium, calcium, magnesium, barium, or

to where R R and R can be the same or different and each can be hydrogen, alkyl of 1 through 4 carbon Rate 3 week Average Yield Per Plant at 4 wks kg/ha Response Rating Number of Fruit Wt. of Fruit g.)

1.1 20. DF 0 .27 1X. ll, DF 0 0 .07 0 2 1.8 0 0 16 45.9

B. Tiny Tim tomatoes with flower buds present were sprayed as above. One plant was treated at each rate and results are indicated below:

atoms, or hydroxy alkyl of 2 through 4 carbon atoms; and R is hydrogen, alkyl of 1 through 12 carbon atoms, or benzyl; R and R can be taken Rate Res nse Ratings Number of Fruit Per Plant kg/ha l9 ys 47 Days 19 Days 47 Days 73 Days l.l 3C, 25 2C, 1A 0 0 0 .27 2C, 1C. 2A 0 O I .07 0 3A 0 0 l2 0 O 0 5 21 wherein R, is alkyl of 1 through 8 carbon atoms, cycloalkyl of 3 through 8 carbon atoms, cycloalkylalkyl of 4 through 7 carbon atoms, alkenyl of 3 through 4 carbon atoms, alkynyl of 3 through 4 carbon atoms, benzyl or where Y is hydrogen, halogen, alkyl of 1 through 4 carbon atoms, nitro, alkoxy of 1 through 4 carbon atoms, alkylthio of 1 through 4 carbon atoms, cyano or trifluoromethyl, and

Z is hydrogen, halogen, methyl, ethyl, nitro, alkoxy of 1 through 4 carbon atoms, or alkylthio of 1 through 4 carbon atoms; and Q is hydrogen, halogen or methyl; R is hydrogen, or a group -AC ll 0 together to form a ring that is (CH-;. O(Cl-l or (Cl-l where n is 4-6 and R and R are H;

R; is SR or OR, where R, is alkyl of 1 through 6 carbon atoms, cycloalkyl of 3 through 6 carbon atoms, alkenyl of 3 through 4 carbon atoms, alkynyl of 3 through 4 I carbon atoms, or benzyl, and

X and X are oxygen or sulfur.

2. A compound of claim .1 wherein R is alkyl of 3 through 6 carbon atoms or alkenyl of 3 through 4 carbon atoms;

R is hydrogen;

R is SR or 0R where R4 is alkyl of 1 through 6 carbon atoms or alkenyl of 3 through 4 carbon atoms; and

X, and X2 are oxygen.

3. A compound of claim 1 wherein R is alkyl of 3 through 4 carbon atoms;

R is hydrogen;

R3 is SCH SC H OCH or OC H and X, and X2 are oxygen.

4. The compound of claim 1 which is 3-tert-butyl-6- methylthio-s-triazine-2,4( lH,3H )-dione.

5. The compound of claim 1 which is 3-sec-butyl-6- methylthio-s-triazine-Z,4( ll-l,3H)-dione.

6. The compound of claim 1 which is 3-isopropyl-6- methylthio-s-triazine-2,4( lH,3H)-dione.

7. The compound of claim 1 which is 3-isopropyl-6- methoxy-s-triazine-2,4( 1H,3H)-dione 8. The compound of claim 1 which is 3-isopropyl-6- ethoxy-s-triazine-2,4( ll-l,3H)-dione.

9. Compound of claim 1 wherein R, is phenyl or substituted phenyl.

10. Compound of claim 9 wherein Y is hydrogen, halogen or methyl, Z is halogen and Q is hydrogen.

11. Compound of claim 1 which is 3-(4- 

1. A COMPOUND OF THE FORMULA
 2. A compound of claim 1 wherein R1 is alkyl of 3 through 6 carbon atoms or alkenyl of 3 through 4 carbon atoms; R2 is hydrogen; R3 is SR4 or OR4 where R4 is alkyl of 1 through 6 carbon atoms or alkenyl of 3 through 4 carbon atoms; and X1 and X2 are oxygen.
 3. A compound of claim 1 wherein R1 is alkyl of 3 through 4 carbon atoms; R2 is hydrogen; R3 is SCH3, SC2H5, OCH3, or OC2H5; and X1 and X2 are oxygen.
 4. The compound of claim 1 which is 3-tert-butyl-6-methylthio-s-triazine-2,4(1H,3H)-dione.
 5. The compound of claim 1 which is 3-sec-butyl-6-methylthio-s-triazine-2,4(1H,3H)-dione.
 6. The compound of claim 1 which is 3-isopropyl-6-methylthio-s-triazine-2,4(1H,3H)-dione.
 7. The compound of claim 1 which is 3-isopropyl-6-methoxy-s-triazine-2,4(1H,3H)-dione
 8. The compound of claim 1 which is 3-isopropyl-6-ethoxy-s-triazine-2,4(1H,3H)-dione.
 9. Compound of claim 1 wherein R1 is phenyl or substituted phenyl.
 10. Compound of claim 9 wherein Y is hydrogen, halogen or methyl, Z is halogen and Q is hydrogen.
 11. Compound of claim 1 which is 3-(4-chlorophenyl)-6-methylthio-s-triazine-2,4(1H,3H)-dione.
 12. Compound of claim 1 which is 3-(4-chlorophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione.
 13. Compound of claim 1 which is 3-(4-bromophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione.
 14. Compound of claim 1 which is 3-(3,4-difluorophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione.
 15. Compound of claim 1 which is 3-(4-methylphenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione.
 16. Compound of claim 1 which is 3-(2-chlorophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione.
 17. Compound of claim 1 which is 3-(4-fluorophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione.
 18. Compound of claim 1 which is 3-(2,4-dichlorophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione.
 19. Compound of claim 1 which is 3-(2-methylphenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione. 